Reproducible Green Syntheses Using Hybrid Sol-Gel Catalysts.

Referring to selected examples of reproducible green syntheses using hybrid sol-gel catalysts of the SiliaCat series from different doctoral theses and research works published between 2015 and early 2024, this study briefly illustrates how said catalysts have been applied in a number of green synthetic methods of significant industrial relevance. This shows evidence that the nanochemistry "bottom-up" sol-gel approach based on catalytic species entrapped in organically modified silicas as effective and versatile heterogeneous catalysts developed between the late 1990s and 2010 has succeeded. Subsequent developments will show how the use of said materials in automated syntheses, supplying data to machine learning algorithms actually leads to faster and cheaper optimization of the reaction conditions. Said progress ultimately will further accelerate industrial uptake of heterogeneous catalysis under flow in the fine chemical industry whose reluctance to change processes was due to the need to replace financially amortized (and expensive) production plants.

The Role of the Journal Impact Factor in Chemistry Research.

The journal impact factor (JIF) is a skewed metrics whose value is dictated by just a few highly cited articles. Therefore, the use of the JIF to evaluate journals, scholars, or research institutes is flawed. Still, the JIF continues to play a central role in evaluating scholarship in chemistry, the most reluctant amid scientific disciplines to embrace the principles of open science. This study investigates the origins of this social behavior, and suggests avenues to improve scholarly communication in the chemical sciences following the example of the life sciences.

Red Orange and Bitter Orange IntegroPectin: Structure and Main Functional Compounds.

DRIFT, HPLC-MS, and SPME-GC/MS analyses were used to unveil the structure and the main functional compounds of red (blood) orange (Citrus sinensis) and bitter orange (Citrus aurantium). The IntegroPectin samples show evidence that these new citrus pectins are comprised of pectin rich in RG-I hairy regions functionalized with citrus biophenols, chiefly flavonoids and volatile molecules, mostly terpenes. Remarkably, IntegroPectin from the peel of fresh bitter oranges is the first high methoxyl citrus pectin extracted via hydrodynamic cavitation, whereas the red orange IntegroPectin is a low methoxyl pectin. C. aurantium IntegroPectin has a uniquely high concentration of adsorbed flavonoids, especially the flavanone glycosides hesperidin, naringin, and eriocitrin.

Protective, Antioxidant and Antiproliferative Activity of Grapefruit IntegroPectin on SH-SY5Y Cells.

Tested in vitro on SH-SY5Y neuroblastoma cells, grapefruit IntegroPectin is a powerful protective, antioxidant and antiproliferative agent. The strong antioxidant properties of this new citrus pectin, and its ability to preserve mitochondrial membrane potential and morphology, severely impaired in neurodegenerative disorders, make it an attractive therapeutic and preventive agent for the treatment of oxidative stress-associated brain disorders. Similarly, the ability of this pectic polymer rich in RG-I regions, as well as in naringin, linalool, linalool oxide and limonene adsorbed at the outer surface, to inhibit cell proliferation or even kill, at high doses, neoplastic cells may have opened up new therapeutic strategies in cancer research. In order to take full advantage of its vast therapeutic and preventive potential, detailed studies of the molecular mechanism involved in the antiproliferative and neuroprotective of this IntegroPectin are urgently needed.

CytroCell: Valued Cellulose from Citrus Processing Waste.

Isolating cellulose from citrus processing waste without employing chemicals has so far been an unfulfilled goal of chemical research applied to the valorization of a widely available biowaste, annually totaling >100 million tonnes. We have applied hydrodynamic cavitation using a Venturi-type reactor for the extraction of all valued bioproducts of industrial citrus processing waste in water only, directly on a semi-industrial scale. After reporting the discovery of IntegroPectin in the soluble fraction of the aqueous extract, we now report the isolation of a cellulosic material in the water-insoluble fraction of cavitated lemon and grapefruit processing waste. Named "CytroCell", the material is cellulose of low crystallinity, high porosity, good water holding capacity and good dispersibility in water. These properties open the route to mass-scale production of a useful functional material from a cheap and abundant biowaste.

Volatile Compounds of Lemon and Grapefruit IntegroPectin.

An HS-SPME GC-MS analysis of the volatile compounds adsorbed at the outer surface of lemon and grapefruit pectins obtained via the hydrodynamic cavitation of industrial waste streams of lemon and grapefruit peels in water suggests important new findings en route to understanding the powerful and broad biological activity of these new pectic materials. In agreement with the ultralow degree of esterification of these pectins, the high amount of highly bioactive α-terpineol and terpinen-4-ol points to limonene (and linalool) decomposition catalyzed by residual citric acid in the citrus waste peel residue of the juice industrial production.

Look Better: Single Atoms in Chemistry and Single Atoms in Physics.

Fostering fruitful collaboration between chemistry and physics scholars, the analysis of the differences in the practical approach to single atoms in chemistry and in physics affords a number of conceptual outcomes pointing to a more balanced and useful relationship between chemistry and physics.

An Industry in Transition: The Chemical Industry and the Megatrends Driving Its Forthcoming Transformation.

Significant product and process innovation is taking place in the chemical industry. Rather than making bold predictions, this Essay emphasizes that this change, due to impact both main segments of the industry, is driven by societal megatrends concerning the environment, health, and energy which permeate societies on a global scale.

Que faire? A Bioeconomy and Solar Energy Institute at Italy's Research Council in the Context of the Global Transition to the Solar Economy.

Driven by insight for which new research and education requires new institutional organisation, and drawing on two decades of research and educational efforts, we devise the profile and activities of a new bioeconomy and solar energy institute at Italy's Research Council. We further articulate the institute's activities suggesting avenues on how to deploy sound and giving more useful research, education and policy advice in these crucial fields for making tomorrow's common development sustainable. The outcomes of the study are of general interest, because the transition to a solar economy is of intrinsic global nature and the challenges involved are similar in many countries.

Layer-by-layer assembly of versatile nanoarchitectures with diverse dimensionality: a new perspective for rational construction of multilayer assemblies.

Over the past few decades, layer-by-layer (LbL) assembly of multilayer thin films has garnered considerable interest on account of its ability to modulate nanometer control over film thickness and its extensive choice of usable materials for coating planar and particulate substrates, thus allowing for the fabrication of responsive and functional thin films for their potential applications in a myriad of fields. Herein, we provide elaborate information on the current developments of LbL assembly techniques including different properties, molecular interactions, and assembly methods associated with this promising bottom-up strategy. In particular, we highlight the principle for rational design and fabrication of a large variety of multilayer thin film systems including multi-dimensional capsules or spatially hierarchical nanostructures based on the LbL assembly technique. Moreover, we discuss how to judiciously choose the building block pairs when exerting the LbL assembly buildup which enables the engineering of multilayer thin films with tailor-made physicochemical properties. Furthermore, versatile applications of the diverse LbL-assembled nanomaterials are itemized and elucidated in light of specific technological fields. Finally, we provide a brief perspective and potential future challenges of the LbL assembly technology. It is anticipated that our current review could provide a wealth of guided information on the LbL assembly technique and furnish firm grounds for rational design of LbL assembled multilayer assemblies toward tangible applications.

Nanoflower-Like Bi2 WO6 Encapsulated in ORMOSIL as a Novel Photocatalytic Antifouling and Foul-Release Coating.

Herein, the first multi-purpose antifouling and foul-release photocatalytic coating based on ORMOSIL thin films doped with nanoflower-like Bi2 WO6 is described. Irradiation with visible light of the new films immersed in water produces significant amounts of H2 O2 by photocatalytic oxidation of water, and allows the degradation of (bio)organic pollutants at the outer surface of the xerogel film.

Industrial Applications of Gold Catalysis.

Gold catalysis has recently found its first large-scale applications in the chemical industry. This Minireview provides a critical analysis of the success factors and of the main obstacles that had to be overcome on the long way from the discovery to the commercialization of gold catalysts. The insights should be useful to researchers in both academia and industry working on the development of tomorrow's gold catalysts to tackle significant environmental and economic issues.

Environmentally benign sol-gel antifouling and foul-releasing coatings.

Biofouling on ships and boats, characterized by aquatic bacteria and small organisms attaching to the hull, is an important global issue, since over 80000 tons of antifouling paint is used annually. This biofilm, which can form in as little as 48 hours depending on water temperature, increases drag on watercraft, which greatly reduces their fuel efficiency. In addition, biofouling can lead to microbially induced corrosion (MIC) due to H2S formed by the bacteria, especially sulfate-reducing bacteria. When the International Maritime Organization (IMO) international convention banned the use of effective but environmentally damaging coatings containing tributyl tin in 2008, the development of clean and effective antifouling systems became more important than ever. New nonbiocidal coatings are now in high demand. Scientists have developed new polymers, materials, and biocides, including new elastomeric coatings that they have obtained by improving the original silicone (polydimethylsiloxane) formulation patented in 1975. However, the high cost of silicones, especially of fluoropolymer-modified silicones, has generally prevented their large-scale diffusion. In 2009, traditional antifouling coatings using cuprous oxide formulated in copolymer paints still represented 95% of the global market volume of anti-fouling paints. The sol-gel nanochemistry approach to functional materials has emerged as an attractive candidate for creating low fouling surfaces due to the unique structure and properties of silica-based coatings and of hybrid inorganic-organic silicas in particular. Sol-gel formulations easily bind to all types of surfaces, such as steel, fiberglass, aluminum, and wood. In addition, they can cure at room temperature and form thin glassy coatings that are markedly different from thick silicone elastomeric foul-releasing coatings. Good to excellent performance against biofouling, low cure temperatures, enhanced and prolonged chemical and physical stability, ease of application, and the waterborne nature of sol-gel coatings all support the diffusion of these paints to efficiently reduce the accumulation of fouling layers on valued surfaces immersed in marine or fluvial waters. Furthermore, sol-gel glassy coatings are transparent and can be effectively applied to optical devices, windows, and solar panels used in lake, fluvial, or marine environments. Sol-gel technology is eminently versatile, and the first generation sol-gel paints have already shown good performance. Even so, vast opportunities still exist for chemists to develop novel sol-gel derived coatings to both prevent biofouling and enhance the hydrodynamic properties of boat and ship hulls. Moreover, researchers have prepared and applied multifunctional sol-gel coatings providing protection against both biofouling and corrosion. They have tested these in the marine environment with good preliminary results. In this Account, we discuss some of our new strategies for the controlled functionalization of surfaces for the development of efficient antifouling and foul-releasing systems and summarize the main achievements with biocidal and nonbiocidal sol-gel coatings. We conclude by giving insight into the marine coatings and sol-gel products markets, providing arguments to justify our conclusion that the sol-gel coatings technology is now a mature platform for the development of economically viable and environmentally friendly antifouling and foul-release formulations of enhanced performance.

Advancing Nanochemistry Education.

The chemical approach to nanotechnology that has emerged in the last three decades has proved to be extremely fertile. As chemistry increasingly turns into nanochemistry, and renewable solar energy available in sunlight and in biomass emerges as the main energy and raw materials source available to mankind, effective teaching of nanochemistry becomes increasingly important. This Viewpoint identifies the requirements of a short course aimed to provide future scholars with the conceptual foundations, and a clear perspective, of an important discipline which turned out to be the enabler of nanotechnology.

Artificial photosynthesis over graphene-semiconductor composites. Are we getting better?

Tremendous interest is devoted to fabricating numerous graphene (GR)-semiconductor composites toward improved conversion of solar energy, resulting from the observation that the photogenerated electrons from semiconductors (e.g., TiO2, CdS) can be readily accepted or shuttled in the two-dimensional (2D) GR sheet. Yet although the hunt is on for GR-semiconductor composite based photoredox applications that aim to exploit the remarkable electronic conductivity of GR, the work necessary to find out how it could best be harnessed to improve the photocatalytic performance of semiconductors remains scanty. In this review, we highlight a few problems associated with improving the photocatalytic performance of semiconductors via methodological coupling with GR. In particular, we address strategies for harnessing the structure and electronic conductivity of GR via strengthening the interfacial contact, optimizing the electronic conductivity of GR, and spatially optimizing the interfacial charge carrier transfer efficiency. Additionally, we provide a brief overview of assembly methods for fabricating GR-semiconductor composites with controllable film infrastructure to meet the requirements of practical photocatalytic applications. Finally, we propose that, only with the principle of designing and understanding GR-semiconductor composites from a system-level consideration, we might get better at imparting the power of GR with unique and transformative properties into the composite system.

Nanochemistry-derived Bi2WO6 nanostructures: towards production of sustainable chemicals and fuels induced by visible light.

Low cost and easily made bismuth tungstate (Bi2WO6) could be one of the key technologies to make chemicals and fuels from biomass, atmospheric carbon dioxide and water at low cost using solar radiation as an energy source. Its narrow band gap (2.8 eV) enables ideal visible light (λ > 400 nm) absorption. Yet, it is the material's shape, namely the superstructure morphology wisely created via a nanochemistry approach, which leads to better electron-hole separation and much higher photoactivity. Recent results coupled to the versatile photochemistry of this readily available semiconductor suggest that the practical application of nanochemistry-derived Bi2WO6 nanostructures for the synthesis of value-added fine chemicals and fuel production is possible. We describe progress in this important field of chemical research from a nanochemistry viewpoint, and identify opportunities for further progress.

Sol-gel microencapsulation of odorants and flavors: opening the route to sustainable fragrances and aromas.

The sol-gel approach to encapsulate fragrance and aroma chemicals in porous silica-based materials has the potential to afford odorant and flavoured materials with novel and unique beneficial properties. Amorphous sol-gel SiO2 is non-toxic and safe, whereas the sol-gel entrapment of delicate chemicals in its inner pores results in pronounced chemical and physical stabilization of the entrapped actives, thereby broadening the practical utilization of chemically unstable essential oils. Reviewing progress in the fabrication of diverse odorant and flavoured sol-gels, we show how different synthetic strategies afford advanced materials suitable for practical application with important health and environmental benefits.

Clean and fast cross-coupling of aryl halides in one-pot.

Unsymmetrically coupled biaryls are synthesized in high yield starting from different aryl bromides and bis(pinacolato)diboron by carrying out the Miyaura borylation reaction followed by the Suzuki-Miyaura reaction in the same reaction pot over 1-2 mol % SiliaCat DPP-Pd. The SiliaCat DPP-Pd catalyst is air-stable and the method does not require the use of inert conditions. The use of non-toxic isopropanol or 2-butanol as reaction solvent further adds to the environmental benefits of this new green synthetic methodology.

Reproducibility in chemistry research.

Chemistry is a reproducible science whose pillars - synthesis and analysis - actually comprise a huge collection of highly reproducible experimental methods to synthesize and analyze substances. The historical development of chemistry, furthermore, shows that reproducibility of methods has been the companion of novelty and creative innovation. The "publish or perish" principle dominating global academia since over two decades, however, intrinsically contributes to the publication of non-reproducible research outcomes also in chemistry. A study on reproducibility of chemistry research seems therefore timely, especially now that chemists are slowly but inevitably adopting open science and its tools such as the preprint, open access, and data sharing. We conclude presenting three simple guidelines for enhanced publication of research findings in chemistry.

Anti-Apoptotic and Anti-Inflammatory Properties of Grapefruit IntegroPectin on Human Microglial HMC3 Cell Line.

In this study, we investigated the beneficial effects of grapefruit IntegroPectin, derived from industrial waste grapefruit peels via hydrodynamic cavitation, on microglia cells exposed to oxidative stress conditions. Grapefruit IntegroPectin fully counteracted cell death and the apoptotic process induced by cell exposure to tert-butyl hydroperoxide (TBH), a powerful hydroperoxide. The protective effects of the grapefruit IntegroPectin were accompanied with a decrease in the amount of ROS, and were strictly dependent on the activation of the phosphoinositide 3-kinase (PI3K)/Akt cascade. Finally, IntegroPectin treatment inhibited the neuroinflammatory response and the basal microglia activation by down-regulating the PI3K- nuclear factor kappa-light-chain-enhancer of activated B cells (NF-kB)- inducible nitric oxide synthase (iNOS) cascade. These data strongly support further investigations aimed at exploring IntegroPectin's therapeutic role in in vivo models of neurodegenerative disorders, characterized by a combination of chronic neurodegeneration, oxidative stress and neuroinflammation.